Benzo(h)quinolin-ols as azine cyan color formers



Sept. 13, 1955 v. TULAGIN Er AL 2,717,831

BENZO(H) QUINOLIN-'OLS AS AZINE CYAN COLOR FORMERS Filed Feb. 24, 19539- (7-cARBoxY 2 NAPHTHY AMINOBENzo (h) QUlNoLlN e-oL-xsULFomc ACIDa-METHYL 4, 4f-DIHYDRoxY-v,

a, BENzoQulNoLINE 40 60 8O 600 2O 40 60 8O 700 INVENTORS VSEVOLODTULAGIN ROBERT F. COLES BY 7 lhalide emulsion with, inter alia,

United States Patent BENZOGDQUINOLIN-ULS AS AZINE CYAN COLOR FORMERSVsevolod Tulagin, Binghamton, and Robert F. Coles, Vestal, N. Y.,assignors to General Aniline & Fiim Corporation, New York, N. Y., acorporation of Delaware Application February 24, 1953, Serial No.338,396 25 Claims. (Cl. 9S-6) acid in the presence of a color activemethylene group, like. Among the color droxyl groups, the patenteesrefer to S-benzene sulfonylamino naphthol, 3sulfo 6 aminonaphthol, 8hydroxy quinoline and the like. It is apparent that in these colorformers the position para to the phenolic hydroxyl group l isunsubstituted, and that coupling inevitably takes place in suchpara-position. It has been our experience that where such para-couplingtakes place between the phenolic color former and the oxidation productsof an azine developer, a magenta azine ydye image is always formed.

The azine dyes produced from available couplers are satisfactory for theyellow and magenta images. In I quite brilliant yellows and magentas.However, available couplers for the cyan have posed a diicult problemboth fromV the standpoint of speed of coupling and the brilliancy of thedyesy produced.

Considerable work has been done in an eifort to solve this problem. Thiswork has led to the selection, inter ala,`as cyan azine color formers ofbenzo(h). and (gf)- quinolines. The use of such couplers is described inon October 10, 1950, to V. This patent describes benzofollowing:

U. S. P. 2,525,502, granted Tulagin and W. A. Schmidt. quinolinesystems, such as the (The arrow in each formula indicates that thebenzoquinoline systems couple ortho to the phenolic hydroxyl group-l Itwill be evident that each of the above systems retwo auxochromic groups.These two groups are essential, since otherwise it is impossible to.obtain coupling of the color former with the oxidation products of anazine developer.

. 2,525,502. It has high coupling speed. For example, even when using4,6- metanilic acid the couplers of U. S. P. 2,525,502 do not produce acyan dye image at once. On the contrary, color development gives a deepbrown stain which becomes cyan only on prolonged washing oracidification.

is far off the standards of brilhancy needed for the cyan dye images ina commercial multilayer color tilm.

We have now discovered a class of benzo (h)quinolines dye imagesobtained on color development. benzo(h)quinoiines are those in which the5- tion is substituted by hydroxyl, primary amino or a sulfon- These Thebenzo(h)quinolines contemplated herein, as cyan azine color formers, maybe more precisely defined as having the following constitution:

7 s Y in which Z is hydrogen, hydroxyl, amino, such as -NH2,

aliphatic amino, i. e., methylamino, ethylamino, butylamino, decylamino,dodecylamino, tetradecylamino, octade'cylamino, and the like, aromaticamino, i. e., phenylamino, a-naphthylamino, -naphthylamino, toluylamino,carboxy naphthylamino, sulfo--naphthylamino, and the like, heterocyclicamino, i. e., pyridylamino, quinolylamino, 4,6-dimethylamino-vtriazinylamino and the like, acylamino, such as aliphatic carbonamido,i. e., acetylamino, propionylamino, butyrylarnino, myristoylamino,stearoylamino, acetyl-N-methylamino, acetyl- N- butylamino,myristoyl-N-decylamino, stearoyl-N-propylamino, acetyl-N-phenylamino,butyl-N-a-naphthylamino, stearoyl-Ntoluylamino and the like, aromaticcarbonamido, i. e., benzoylamino, a-naphthoylamino, I-naphthoylamino,salicoylamino, benzoyl-N-rnethylamino, salicoyl- N-propylamino,benzoyl-N-phenylamino, a-naphthoyl-N- toluylamino and the like,aliphatic sulfonylamino, e., 6-p-toluenesulfoamidobenzo(h)quinolin9olrnethylsulfonylamino, ethylsulfonylamino, octadecylsul-5-aminobenzo(h)quinolin-S-ol fonylarnino, tetradecylsulfonylamino,ethylsulfonyl N- Benzo(h) quinolin-5,9diol ethylarnino,octadecylsulfonyl-N propylamino and the 9 (8 carboxymethoxy 2naphthylamino)benzo(h) like, aromatic sulfonylamino, i. e.,benzenesulfonylamno, quinolin-6-ol-X-sulfonic acid of the followingformula: a-naphthylsulfonylamino, m-nitrobenzenesulfonylamino, C O OH rnaminobenzenesulfonylamino, benzenesulfonyl N- E methylamino,benzenesulfonyl-N-phenylarnno, toluenel z sulfonyl-N-methylarnino andthe like, and Y is OH, NH2, O

or -NHSO2R, in which R is an aliphatic radical, such as l0 H methyl,ethyl, propyl, butyl, decyl, dodecyl, tetradecyl, k/ N octadecyl and thelike, or an aromatic radical such as phenyl, nitrophenyl, aminophenyl,naphthyl, toluyl and the like.

Examples of color formers within the stated category l5 HOQS OH l are:9-methylsulfonylaminobenzo (h)quio1in6-ol X sulfonic acid9-p-toluenesulfonyl N rnethylarninobenzo(h)quinolin-6-methylsulfonylaminobenzo (h) quinolin-9-ol9-rnethylsulfonylamino-6-aminobenzo (h) quinoline Benzo(h)quinolin5o1.Benzo (h) quinolin--ol Benzo (h) quinolin-6,9diol 20 9-aminobenzo (h)quinolin-6-ol 9-acetylaminobenzo(h)quinolin-6-ol9arninobenzo(h)quinolin-6-ol- -sulfonic acid 69jd1amfn0bezoih)quufime H9acetylarninobenzo(h) quinolin--ol-X-sulfonic acid 912 [7 (3 Sulfo'sOctadecylsuifonyiammo 9-p-toluenesulfonylaminobenzo(h) quinoline 6 ol X-2r mthyl) phenyicaibam'yi]naphthylaminobenzo(h)quinsulfonic acid 0ol1n6olXsulfon1c acid of the followlng formula:9octadecylsulfonylaminobenzo(h)quinolin 6 ol X- sulfouic acid9-tetradecylsulfonylaminobenzo(h)quinolin 6 ol X- 0 H (fm H O sulfunicacid .w ll l lT H H 9 (3 tetradecanoylaminobenzosulfonyl)aminobenzo-CSHWCN" I\C N (h) quinolin-6-ol-X-sulfonic acid of the followingformula:

m do H rito s \0H Cl 3 E i 35 l0-arninozenzo(h)quinolin-6-ol. -SOziI-The above compounds can be made while utilizing i conventional chemicalprocesses. For instance, the NH benzo(h)quiuoline ring structure isdeveloped through o 40 the reaction of a selected aminonaphthalenesulfonic H SOSH H acid, glycerine, a dehydrating agent such as sulfuricacid 4 i and an oxidizing agent such as picric acid. Hydroxyl 9-(3'nitrobenzenesulfonyl)aminobenzo (h) quinolin 6- gfOUPS may besubstituted for SUifO gfOuPS ihlOUgh alka- O1 X Su1f0nic acid linefusion. Amino groups may be introduced via hy- 9 (3aminobenzenesulfonyl)aminobenzo(h)quinolin 45 droxy groups by thewell-known Bucherer reaction. 6 01-X su1f0ni acid Actylation is effectedby the use of acid chlorides in the 9-(7carboxy 2naphthyl)aminobenzo(h)quinoline 6- Presence 0f all acid binding agentSuch aS YPfidiIleol-X-sulfonic acid It will be appreciated that severalof the compounds 9-2[7(1octadecyl 5" sulfo 2" benzimidazoyl) listedabove contain only a single auxochromic group. phenylcarbamyllnaphthylaminobenzo(h) quinolin 6- 50 Despite this fact, and quite unlikethe couplers of U. S. P. ol-X-sulfonic acid of the following formula:2,525,502 which bear no substituent group in the 5- or /N Ei 1i i Y iHOaS- N \C-NHC o@ N/ (i) aHa-l l sich 0H9-methylaminobenzo(h)quinolin--ol 1 -position, the couplers have veryhigh coupling speed. 9-(4,6-dirnethylamino-triazinylarnino)-6-ol Xsulfonic This is apparently attributable to the rather remarkable acidof the following formula: properties provided by the double bond in the5- -posial.; tion. It is to be pointed out, however, that the mosteffective couplers are those in which an auxochrome E also appears inthe 9-positiort probably because of the 1LT resonance thus set up. CH3HN//N\/ Many of the color formers listed above contain a L l i 70 groupwhich renders the color formers fast to diifusion in the photographicemulsion. When such a coupler is selected, it must be used in theemulsion since it would SO/BH E be incapable of diffusing from thedeveloper into the emulsion except as a surface dyeing. Where thecouplers NHCHa do not contain such a non-diffusing group they may be-aminobenzo (h) quinolin-9-ol 75 employed either in the developer or inthe emulsion.

. The color developers which are employed in our process are of the4,6-diamino metanilic class. Compounds within this category aredescribed in U. S. P. 2,486,440 and 2,611,785. Examples of suchdevelopers are 4 (-hydroxyethyamino) 6 (4 carboxymethoxyphenylamino)metanilic acid, 4-(hydroxymethylamino) 6(4methoxypheny1amino)metanilic acid, 4,6-di(-hydroxyethylamno)metanilic acid,4-hydroxyethylamino-6- phenylamino metanilic acid and the like.

The invention is further explained with reference to the accompanyingself-explanatory drawing which depicts the brlliancy of the dyesobtained from 9-(7carboxy2 naphthyl)aminobenzo(h)quinolin-6-ol-sulfonicacid, on the one hand, and 2-methyl-4,4'dihydroxy7,8benzo quinoline, onthe other hand, while utilizing as the developer4-hydroxyethylamino-6-anilo metanilic acid. In the drawing the abscissais plotted as wave length in millimicrons land the ordinate as log ofexposure. lt is believed that this drawing speaks for itself inestablishing the superior brilliancy of our cyan azine dye images.

The invention is illustrated by the following examples in which theparts are by weight unless otherwise stated. It is to be understood thatthese examples are not restrictive of the invention.

PREPARATION OF COLOR FORME-RS Example I BENZ() (H) QUINOLIN--OL Ninetyparts of 4-amino-Z-naphthalenesulfonic acid, 24.0 parts of glycerine,180 parts of concentrated sulfuric acid and 16.5 parts of picric acidwere thoroughly mixed and slowly heated to 140 C. at which point anexothermic reaction started. Tie temperature was maintained between140-145o C. by means of external cooling until no more heat was evolved,and then at the same temperature for another minutes by the applicationof heat. The mixture was cooled to 120 C. and poured into 1500 parts ofice water. The precipitated solid was collected by filtration andthoroughly washed with water. The material so obtained was dissolved inhot concentrated sodium acetate solution, treated with Nuchar andfiltered. Upon cooling the filtrate, the sodium salt separated in theform of dark brown crystals. This' substance was collected byfiltration, redissolved in water and decolorized. The `filtered solutionwas acidified strongly with hydrochloric acid and the solid collected byfiltration. This material can be further purified by recrystallizationof the sodium salt from water. The product consists of white crystallineneedles weighing 59 grams and amounting to a yield of 52%. Thissubstance is fused with sodium hydroxide and converted to 5-hydroxybenzo(h) quinoline.

Example Il BENZO (H) QUINOLIN-G-OL This compound was prepared accordingto the procedure of Example I, while starting froml-aminonaphthalene-4-sulfonic acid.

Example III BENZO (H) QUINOLIN-6,9DIOL Into a 500 cc. metal beaker wereplaced 75 grams of potassium hydroxide and grams of sodium hydroxide.The temperature was raised to 200 C. and 25 grams ofbenzo(h)quinolin-6,9disulfonic acid was introduced. After the foaminghad subsided, the bath temperature was raised to 2404250o C. for 15minutes and then to 340 C. for 5 minutes. The mixture was cooledsomewhat and then treated cautiously with ice until an .aqueous solutionof about 300 cc. total volume was obtained. The solution was neutralizedwith acetic acid and cooled, and the precipitated black tar extractedwith boiling water containing 25-50 cc. of concentrated hydrochloricacid. The insoluble material was removed by filtering the hot Crasolution through a fiuted filter and the cooled filtrate decolorized andneutralized with ammonia. The precipitated dark brown oil graduallybecame crystalline' up'on standing.

The benzo(h)quinolin-6,9disulfonic acid used above was prepared asfollows:

Into a 500 cc. 3-necked fiask, equipped with a `stir rer, a refluxcondenser and a thermometer were placed in the order named and withmixing after each addition grams of purified4-aminonaphthalene-1,6-disulfonic acid, grams of glycerine, 7.5 grams ofpicric acid and 50 grams of cold concentrated sulfuric acid.

The mixture was heated to -140" C., whereupon the reaction becameuncontrollable and the temperature rose to 175-180 C. The refiuxcondenser was removed and the water formed allowed to distill outfreely. Upon completion of the vigorous .exothermic reaction, thecontents of the tiask set to a black tar. This material was extractedfor several hours with 250 cc. of water, and the black insoluble solidcollected by filtration. The filtrate was discarded and the precipitateextracted with about 500 cc. of saturated boiling sodium acetatesolution. The insoluble black tar was removed by filtration anddiscarded. Upon acidification of the filtrate with concentratedhydrochloric acid, a crystalline solid slowly separated. This solid wascollected by filtration, washed with water, dried and used withoutfurther purification.

The 4-a1ninonaphthalene-1,6,disulfonic acid used asv above was purifiedas follows: i

The material known to commerce as Dahls acid, land consisting of a crudemixture of 4-amir'ionaphthalene-1,67 disultonic acid and4-aminonaphthalene1,7-disulfonic acid,was dissolved in hot water withthe aid of sodium acetate, and the hot solution filtered. The filtratewas treated with a large excess of acetic acid and allowed tocrystaliize. The crystalline material was collected by filtration,washed with ice water and sucked as dry as possible. The still wet cakewas dissolved in hot water with just enough ammonium hydroxide to maltea neutral solution and saturated with calcium chloride until an excessof calcium ion had been introduced. The mixture was maintained at theboiling point until the crystallization of the calcium salt seemed to becomplete (about 1/2 hour).v The hot suspension so obtained was filteredimmediately, the collected calcium salt washed first with hot water andthen with cold water and dried.v

The calcium salt thus obtained was converted to the potassium salt byboiling with an excess of potassium The precipitated calcium carbonatewas removed by filtration, the filtrate acidified with a large excess ofacetic acid and cooled. The crystalline material so obtained was usedwithout further purification.

Example l V Q-AMINOBENZO (H) QUINOLIN-S-OL Seventy grams of thepotassium salt of 9aminobenzo (h)quinolin6sulfonic acid was reacted with`600 grams of 50% potassium hydroxide solution in an autoclave at 265 C.for 10 hours. The reaction mixture was filtered through a sintered glassfunnel and the cake was washed with warm water to dissolve any solublematerial. The combined filtrates were neutralized with hydrochloric acidto a pH of 7, then acidified to a pH of 5-6 with acetic acid, andfinally neutralized to a pH of 7 with ammonium hydroxide. The productwas collected by filtration and washed with water. The washed cake wassuspended in l liter of water and dissolved by the addition of 50 ml. ofconcentrated hydrochloric acid. grams of anhydrous sodium sulfate wasdissolved in 400 ml. of water and added while hot to the acid solutionheated to near boiling. The resulting mixture was then set aside tocrystal.- lize and finally chilled in ice. The separated product wascollected on a Bchner funnel, washed with a small amount of cold water,followed by alcohol, and finally with low boiling petroleum ether anddried. A yield of 54 grams of the product was obtained.

The 9-aminobenzo(h)quinoline6sulfonic acid, used above, was prepared asfollows:

100 grams of 9-hydroxybenzo(h)quinoline--sulfonic acid was suspended in1 liter of 28% ammonium hydroxide containing 100 rnl. of water saturatedwith sulfur dioxide at 15 C. This suspension was reacted in an autoclaveat 250 C. for 24 hours. The resulting reaction mixture was then filteredand the filtrate heated under diminished pressure to remove excessammonia. The residual solution Was again filtered and made alkaline withpotassium hydroxide to a pH of 11, after which it was heated to nearboiling and solid potassium chloride, equivalent to of the total Weight,was added with stirring. The precipitated potassium salt was collectedfrom the chilled solution by filtration and redissolved in approximately1 liter of hot water. The solution was treated with Norit, filtered,reheated, and 10% of its weight of solid potassium chloride was added.The mixture was chilled and the purified potassium salt collected on aBchner funnel. The filter cake Was washed with a small amount of cold10% potassium chloride solution and dried for use as stated above.

The 9-hydroxybenzo(h)quinolin--sulfonic acid, used above, was preparedby the following method:

100 grams of concentrated sulfuric acid was slowly added to 300 grams ofchilled glycerol while keeping the temperature below 70 C. To thismixture was added 8 grams of picric acid (containing 10% of water)followed by 47.8 grams of powdered 8-amino-Z-napl'ithol-5-sulfonic acid.This mixture was intimately stirred until a hornogeneous slurry wasobtained. The slurry was added in small portions to a l-liter,ffl-necked flask fitted with an agitator and thermometer maintained atS-160 C. while the internal reaction temperature was held at 140-145 C.Addition of the slurry was made over an interval of one hour. Afterstirring for an additional 10-15 minutes to insure completeness of thereaction, the mixture was poured into 1 to 1.5 liters of water withstirring.

The precipitated product was collected by filtration and washed wellwith water, and then partially dried by washing with absolute alcohol.The crude cake was then suspended in 500 ml. of dimethylformamide,broken up in a Waring Blender and the resulting suspension transferredto a beaker and heated to 70-80 C. The insoluble material was collectedon a Bchner funnel and washed well with dimethylformamide, followed byabsolute alcohol and then sucked nearly dry.

' Thirty-three grams of anhydrous sodium acetate was dissolved in lliter of water, the filter cake was suspended therein and brought to aboil. The solution was then treated with Norit and filtered. Thefiltrate was again heated, solid sodium chloride equal to 10% of theweight f was added and the resulting mixture stirred well to dissolvethe salt. After chilling in ice for several hours, the precipiatedsodium salt was collected by filtration.

The sodium salt thus obtained was redissolved in 1 liter of water withthe aid of 10% sodium hydroxide solution (to form the more solubledisodium salt), again treated with Norit at near boiling temperature andfiltered. The hot filtrate was aciditied (to Congo paper) withconcentrated hydrochloric acid, cooled to about room temperature and theproduct collected by filtration. The filter cake was washed well withwater, followed by absolute alcohol and low boiling petroleum ether,then dried. The yield of pale yellow product was 50 grams.

The 8-amino-Z-naphthol-S-sulfonic acid was prepared from purified8-amino-2-naphthol by the process of Y German Patent 676,856.

The S-amino-Z-naphthol was prepared from crude 8-amino-2-naphthol asfollows:

100 grams of the crude product was dissolved in 1700 ml. of watercontaining 90 ml. of concentrated hydroand set in a molten metal bathchloric acid. The suspension was heated to boiling by the directintroduction of steam, decolorized with Norit and filtered. Concentratedsodium acetate solution was added to the filtrate until neutral to Congored paper, the solution again brought to boiling and decolorized andfiltered. 900 ml. of ethanol was added to the filtrate and the solutionheated to boiling, after which it was treated with -40 grams ofdecolorizing charcoal for 10-15 minutes and finally filtered into a askcontaining 5-10 grams of solid sodium metabisulite. Steam was passedinto the resulting solution until boiling occurred. 200 ml. ofconcentrated sodium acetate solution was added with stirring and themixture chilled in an ice bath. The product was collected on a largefunnel, washed repeatedly with water, sucked dry and finally dried in avacuum oven at 80 C.

Example V B-ACETYLAMINOBENZO (H) QUINOLIN-S-OL This compound wasprepared by acetylation of 9-aminobenzo(h)quinolin6ol by theSchotten-Baumann reaction while using an excess of acetic anhydride andin the presence of aqueous sodium carbonate.

Example VI 9-AMINOBENZO (H) QUINOLIN--OL-X-SULFONIC ACID To 100 grams of100% sulfuric acid was added, at room temperature and with agitation, 14grams of 9- aminobenzo(h)quinolin-6-ol hydrochloride. The mixture waswarmed gently and then maintained at -60 C. for 3 hours. The mixture waspoured onto 200 grams of ice and the resulting aqueous solution cooled.The crystalline solid so obtained was collected by filtration and washedwith water. The solid was dissolved in dilute sodium bicarbonatesolution, any insoluble material removed by filtration, and the filtrateaciditied with hydrochloric acid, sufficient acid being added to makethe solution about 6 N. The resulting crystalline solid was collected byfiltration, washed with 2 N hydrochloric acid and dried.

Example VII This compound was made by acetylating the product of ExampleVI according to the Schotten-Baumann reaction while utilizing an excessof acetic anhydride in the presence of aqueous sodium carbonate.

Example VIII 9-1?-TOLUENESULFONYLAMINOBENZO (H) QUINOLIN-G-OL-X-SULFONIC ACID by crystallization from water.

Example IX Q-OCTADECYLSULFONYLAMINOBENZO (H) QUINOLIN-(i- OLX-SULFONICACID Into a 500 cc. 3-necked fiask, equipped with an agitator, a refluxcondenser and a dropped funnel were placed 100 ml. of dry pyridine and9.5 grams of 9-aminobenzo(h)-quinolin-6-ol-X-sulfonic acid. The mixturewas stirred and heated for about 30 minutes. A solution of 12.6 grams ofoctadecylsulfonyl chloride in ml. of dry pyridine was added dropwise tothe reflux mixture during a period of l hour and the mixture furtherrefiuxed for 2 hours. The resulting solution was filtered to remove asmall amount of insoluble yellow solid and evaporated as far as possibleat C. and 10 mm. pressure. The residue was dissolved in 300 ml. of Waterand filtered.

The insoluble potassium salt so obtained was dissolved in hot water. Thesolution was treated with resulting suspension was filof purificationwas repeated several the potassium salt was converted to the insolublematerial was dried and dimethylformamide. lected by iltration andthoroughly washed with acetone. This substance was used as anon-diffusing cyan color former without further purification.

Example X 9-TETRADECYLSULFONYLBENZO (H) QUINOLIN-6OLX SULFONIC ACID Intoa 500 cc. 3-necked flask, equipped with an agitator, a Water take-oil?reux condenser and a heating mantle, were placed 75 ml. of pyridine, 50ml. of dry benzene and 8.7 grams of9aminobenzo(h)quinolin-6-ol-X-sulfonic acid. The mlxture was reuxeduntil no more water was apparent in the water separator and then 75 ml.of the mixed solvent was removed by distillation. The solution wascooled to room temperature and 9 grams of tetradecylsulfonyl chloridewas added. The mixture was stirred at room temperature for 2 hours andthen heated to reux for 1 hour. The resulting solution was poured into amixture of concentrated hydrochloric acid and ice. The insoluble solidwas collected by filtration, and dissolved in water with the aid ofsodium hydroxide. A neutral solution Was obtained. This solution wastreated with brine and the insoluble sodium salt was collected byfiltration and crystallized from dilute brine. The solid was redissolvedin hot water with the aid of excess alkali and the mixture renderedstrongly acid with hydrochloric acid. The solid was as the mixturecooled. The solid was collected by Iiltration, washed with acetone anddried. This substance was used as a non-diffusing cyan color formerwithout further purification.

Example XI 9- (3NITROBENZENESULFONYL AMINOBENZO (H0QUINOLIN-G-OL-X-SULFONIC ACID In a 500 cc. 3necked ask, equipped with anagitator and a condenser, were placed 150 m1. of pyridine and 20 gramsof 9-aminobenzo(h) quinolin--ol-X-sulfonic acid. The mixture was heatedto reliux and stirred for l minutes. grams of 3-nitrobenzenesulfonylchloride was introduced in small portions to the Warm suspension duringa period of 15 minutes. The resulting solution was heated with agitationuntil the intense red color had disappeared (about 1 hour). After thepyridine was rewas poured onto a mixture of 200 grams of ice and 300 ml.of water, suliicient sodium hydroxide being added to produce a neutralsolution. The mixture was liltered to remove a small amount of insolublematerial, heated to boiling and treated with 100 ml. of 30% brine.cooling, a iinely dispersed solid was obtained. This material wascollected by filtration and dried, the yield being 24 grams.

Example XII 9- (3AMINOBENZENESULFONYL)AMINOBENZO (H)QUINOLlN6-OLX-SULFONIC ACID The sulfonamide obtained in Example XI wasadded to a solution of grams of sodium hydrosulte in 500 grams of 10%aqueous sodium hydroxide. The resulting yellow solution was filtered,cooled and acidiiied with by filtration, water with the aid of sodiumhydroxide. was reprecipitated by acidification, collected dried and usedwithout further purification. grams.

The product by filtration, Yield-10 Example XIII 9- (3 '-TETRADECANOYLAMINOBENZENESULFONYL) AMINOBENZO (H) QUINOLIN-G-OL-XS ULFONIC ACIDThe amino sulfonamide of Example XII was dissolved 1n 75 ml. ofpyridine. l5 ml. of dry benzene was added and the mixture was reliuxedunder a water take-off con- Example XIV and 9 grams of the hydrochlorideand 9-aminobenzo(h)quinolin-6-ol-X-sulfonic acid. The solution Washeated almost to boiling, 50 grams of sodium metabisullite added, andthe resulting suspension reiluxed for 1/2 hour and diluted with anadditional 100 ml. of water. The mixture was further reiluxed for 2hours and then treated with an additional 50 grams of sodium metabisuliite.

uct was collected, washed with 30% brine, suspended in 500 ml. ofboiling water and treated with hydrochloric acid until acid to Congo redpaper. The suspension was boiled to expel sulfur dioxide and theinsoluble solid was collected by filtration. The material was dissolvedin hot dilute sodium acetate solution, treated with an, excess of aceticacid at the boiling point and liltered hot to remove the insolublestarting material.

l l and dried. This material was used as without further purification.

Example XV 9 2' ['7'-(1"-OCTADECYL-5"-SULFO-2' '-BENZIMDAZOYL) P H E N YL C AR B AMYL]NAPHTHYLAMINOBENZO (H) QUINOLlN-G-OL-X-SULFONIC ACID acyan color former Into a 500 cc. 3-necked flask, equipped with anagitator and a water take-off reflux condenser, were placed 100 ml. ofdry pyridine and 100 ml. of dry benzene, 5 grams of 9(7carboxynaphthyl)aminobenzo(h)quinolin-6-ol- X-sulfonic acid and 5.0grams of l-octadecyl-2(4-amino phenyl)benzimidazole-S-sulfonic acid andthe mixture was refiuxed until no more water was evident in the watertake-off condenser. 100 ml. of the mixed solvent was removed bydistillation. The mixture was then treated with a solution of 0.75 gramof phosphorous trichloride in 25 ml. of dry benzene. The reactionmixture was heated under refiux for 3 hours and the solvents were thenremoved by distillation at 100 C. and 15 mm. pressure. The residualsyrup was dissolved in 100 ml. of water and the solution refiuxed for11/2 hours. Excess 30% brine was added, whereupon the product separatedas a brown gum. This material was redissolved in hot dilute aqueoussodium hydroxide, collected by filtration, washed with water and dried.The product was dissolved in 50 ml. of pyridine, 50 rnl. of aceticanhydride was added and the mixture refiuxed for 15 minutes. The productwas precipitated by the addition of excess acetone, collected byfiltration, washed with acetone and dried.

After refiuxing the substance so obtained for 15 minutes with an excessof 1 N sodium hydroxide solution and reprecipitating by the addition ofhydrochloric acid, the resulting solid was dissolved in hotdimethylformamide and glacial acetic acid was added. Upon cooling, acrystalline substance was collected which was used as `a nondiffusingcyan color former without further purification.

Txample XVI 9,2[7 (3"-SULFO-"-OCTADECYLSULFONYLAMINO-G M E T H Y L)P H ENY L CARBAMYL] NAPHTHYLANHNO- BENZO (H) QUINOLIN-(S-OL-X-SULFONIC ACIDThe procedure for making the above compound is the sante as that ofExample XV, excepting that the benzimidazole-S-sulfonic acid of ExampleXV is replaced by an equivalent quantity of6-myristoylamino-2-amino-toluene-4-sulfonic acid.

Example XVII D-METHYLABIINOBENZO (H)QUINOLIN-GOL A mixture of grams ofbenzo (h)quinolin9ol6sul fonic acid, 130 ml. of 40% aqueousnaphthylamine solution and 20 ml. of saturated aqueous sulfur dioxidesolution was placed in an autoclave and heated at 280 C. for 18 hours.The solution was decanted from the insoluble gum and treated with anexcess of solid potassium hydroxide. The insoluble potassium salts soobtained were collected by filtration, dissolved in water andneutralized by the addition of hydrochloric acid. The mixture wasacidified by the addition of acetic acid. The orange solid whichprecipitated was collected by filtration and extracted with cold diluteaqueous sodium bicarbonate. Any insoluble material was removed bydecantation and filtration. The filtrate was treated with a few drops ofhydrochloric acid and the first gummy precipitate was removed byfiltration. The filtrate was acidified with an excess of acetic acid andthe precipitated orange solid was collected by filtration, washed withwater and dried. The product is 9-methylamino (h) quinolin--sulfonicacid.

9-methylamino (h)quinolin6sulfonic acid was added to grams of 50%aqueous potassium hydroxide and the resulting suspension was heated inan autoclave at 265 C. for 10 hours. After diluting the reaction mixturewith water to 100 ml., the solution was heated to boiling and filteredthrough a layer of Celite to remove the small amount of insolublematerial. The filtrate was acidified with hydrochloric acid and thenmade neutral by the addition of ammonium hydroxide. After the firstgummy precipitate solidified, the substance was collected by filtrationand dissolved in hot dilute hydrochloric acid. The solution was cooled,filtered to remove the small amount of insoluble material and thefiltrate made basic with ammonium hydroxide. The solid thus obtained wascollected by filtration, washed with water, dried and used withoutfurther purification as a cyan color former.

Example XVIII 7CARBOXYBENZO (H) QUINOLIN-G-OL A mixture of 50 grams of7-cyanobenzo(h)quinolin- 6-sulfonic acid and 300 grams of 50% aqueouspotassium hydroxide solution was heated in an autoclave at 265 C. for l0hours. The resulting solution was filtered to remove a small amount ofsuspended extraneous material. The filtrate was treated with ice,partially neutralized by the addition of concentrated hydrochloric acidand the mixture finally brought to a pH of 5-6 by the addition ofglacial acetic acid. The resulting suspension was heated to boiling andfiltered. The product was dissolved in a solution of 40 ml. ofconcentrated hydrochloric acid in 2 liters of water at the boilingpoint. After filtering to remove a small amount of insoluble material,rnl. of a concentrated hydrochloric acid were added to the filtrate. Thesolid obtained upon cooling was collected by filtration and washed withwater. The material was dissolved in 2 liters of boiling watercontaining 30 ml. of concentrated hydrochloric acid and the solutionbrought to a pH of 5-6 by the addition of saturated sodium acetatesolution. The nearly white crystalline solid was collected byfiltration, washed with water and further purified by crystallizationfrom a mixture of dimethylformamide and glacial acetic acid. Yield-18grams.

The 7-cyar1obenzo(h)quinolin-6-sulfonic acid, used above, was preparedas follows:

Into a 3-liter, 3-necked flask, equipped with an agitator and a refluxcondenser, were placed grams of 7- aminobenzo(h)quinolin--sulfonic acid,2 liters of water and 300 ml. of concentrated hydrochloric acid. Themixture was heated to reflux, whereupon all of the solid dissolved. Thesolution was cooled to 20 C. and the resulting suspension was diazotizedby the dropwise addition of a solution of 30 grams of sodium nitrite in125 ml. of water. The light yellow diazonium salt was collected byfiltration and washed with ice water.

The still damp diazonium salt was added slowly to a previously preparedsolution of 40 grams of cuprous cyanide and 64 grams of sodium cyanidein 640 ml. of water. During the addition, the cuprous cyanide solutionwas stirred and maintained at 60-70 C. When the addition was completed(l5 minutes), the mixture was heated for 1/2 hour on a steam bathtreated with 100 grams of solid sodium chloride, cooled and filtered.The solid so obtained was washed with 30% brine until free of cyanide.

The crude 7-cyanobenzo(h)quino1in6sulfonic acid was further purified bydissolving it in a liter of hot water, decolorizing and crystallizing bythe addition of 30% brine. The substance so obtained was dissolved inhot water and the resulting solution treated with 50 ml. of concentratedhydrochloric acid. The product, which crystallized in the form ofyellowish-brown fiakes, was collected by filtration, washed with water,pressed under a rubber dam, washed with methanol and dried. Yield- 100grams.

The 7-aminobenzo(h)quinolin--sulfonic acid was prepared as follows:

Into a 5-liter, 3-necked flask, equipped with an agitator, condenser anda heating mantle were placed 2 liters of water, 5 ml. of glacial aceticacid, and 300 grams of neutralized to a pH of -8 with hydrochlorid acid,and then finally brought to a pH of -6 by the addition of glacial aceticacid. Upon cooling, a crystalline white solid separated which wascollected by filtration, washed with water and dried.

rPhe following procedure was used to form the 7- nitrobenzo hquinolin--sulfonic acid.

Into a 2-liter, 3-necked fiask, equipped with a regulation stirrer andthermometer was placed 700 ml. of concentrated sulfuric acid. 183 gramsof benzo(h)quinolin 6sulfonic acid was added slowly with agitation. Theresulting solution was cooled to 75 C. and treated dropwise with asolution of 52 grams of yellow fuming nitric acid (9.16%), dissolved in75 ml. of concentrated sulfuric acid. After stirring for 1/2 hour at 0C., the reaction mixture was allowed to Warm up to room temperature. Themixture was poured into 2500 grams of ice, the precipitated solidcollected by filtration and thoroughly washed with water. The solid wasdissolved in 3 liters of hot water with the aid of aqueous sodiumhydroxide solution. 200 grams of sodium chloride was added and theresulting suspension was heated to boiling for several minutes and thenfiltered. The solid so obtained represents the isomer whose compositionwas not determined. The filtrate was cooled in an ice bath and thecrystalline solid was collected and washed with brine. Acidification ofthe mother liquor gave an additional small quantity of the samematerial. The line solid so obtained was dissolved in 2 liters of hotwater, the

collected by filtration, pressedunder a rubber darn, washed withmethanol and dried. Yield-167 grams.

Example XIX 9-[2"(426'-DIMETHYLAMINO-1,3,5-TRIAZINYLAMINO) BENZO (H)QUINOLIN-G-OL-X-SULFONIC ACID Into a l-liter, 3-necked flask, equippedwith a stirrer, a reflux condenser and a thermometer and surrounded byan ice bath, were placed' 300 ml. of ice water and 4.75 grams ofpotassium 9-aminobenzo(h)quinolin6ol x-sulfonic acid. A solution of 2.8grams of purified eyanuric chloride in ml. of' acetone was thenintroduced and the mixture was stirred at 0 C. for 1 hour while asolution of .81 gram of potassium hydroxide in 25 ml. of water was addeddropwise at such a rate that the pH was always maintained atapproximately 7. At the end of the above addition, 65 grams of 30%aqueous methylamine solution was introduced and the mixture was heatedon a steam bath for 2 hours. The resulting solution was acidified withhydrochloric acid and the precipitated solid was collected by filtrationand washed with water. The material so obtained was dissolved in hotwater with the aid of just enough sodium hydroxide to cause solution.The solution was decolorized and aqueous sodium chloride solution wasadded until the material just started to crystallize. The suspension wascooled, the crystalline solid collected by filtration, washed with asmall amount of ice water and dried. This substance was used as a cyancolor former without purification.

, 1 4 Example XX 6-AMINOBENZO (H) QUINLIN-S-OL A mixture of 103 grams ofbenzo(h)quinolin6,9diol,

C. was at 210 C. for 10 hours. The autoclave was opened and ml. of watercontain- 6-P-TOLUENESULFONAMIDOBENZO (H) QUINOLIN-9OL Into a l-liter,3necked fiask water separator, and a heating The solid which separatedupon cooling was collected by filtration, and washed with a small amountof cold pyridine. The cake was dissolved in 200 ml. of a 1:1 mixture ofconcentrated ammonium hydroxide in water at 6070 C. Afterdecolorization, the solution was strongly acidified with concentratedhydrochloric acid (about 250 cc.), chilled in ice and the solidcollected by filtration. The yield was 34 grams.

PROCESSING Example XXII 4 hydroxyethylamino 6 phenylamino metanilic acidgrams 1.5 Sodium sulfite do 30 Potassium carbonate do 40 Pyridine cc 12The film is washed, bleached and fixed in the conventional manner toyield a cyan azine dye image of great brilliancy.

Example XXIII The procedure is the same as in Example XXII, exceptingthat the color former employed is that disclosed in Example XV.

Example XXIV A silver bromide emulsion is exposed and color developed ina developer of the following constitution:

Grams 4,6-diphenylamine metanilic acid 1.5 Sodium suliite Potassiumcarbonate Pyridine l2 9-(7- carboxy-2'naphthyl aminobenzo(h) quinolin-6-ol-X-sulfonic acid Water to make l liter.

fixed in the customary A brilliant negative cyan azine dye image Colorof Coupler Formed Dye Benzo(h)quinolin5ol Cyan. Benzo(h)quinolin6ol Do.Benzo(b)quino1in-G,9diol Blue-cyan. 9-Aminobenzo(h)quinoliJ1G-ol Do.Q-Methylaminobenzo(h)qunolin Cyan T-Carboxybenzo (h) qumolm--ol.

It is to be emphasized that when the color coupler is abenzo(h)quinolin9ol, containing in the 6-position, either an amino orsulfonamido group, coupling takes place on the 5 ,6-double bond with theelimination of ammonia on the one hand, or the sulfonamide group on theother hand. Assuming that the same developer is used, then the dyesobtained from the 6-amino and 6-sulfonamido derivatives areidenticalwith those obtained from benzo (h) quinolin-6,9diol.

It will be observed that in referring to certain of the color formersprovided with a sulfo group that the position of such group has beenindicated generally by the letter X. It appears from our experience thatthe sulfo group enters the 7-position of the benzo(h) quinoline.However, since we have been unable to establish this as a definite fact,it is considered preferable to generally indicate the positioning of thesulfo group.

Various modications of the invention will occur to persons skilled inthe art, and we, therefore, do not intend to be limited in the patentgranted except as necessitated by the prior art and the appended claims.

We claim:

l. The process of producing cyan azine dye images by color formingdevelopment which comprises exposing a silver-halide emulsion anddeveloping the same with a 2,4-diamino-aniline developer in the presenceof a color former having the following formula:

2. The process as dened in claim l, wherein the color l@ former is9-(7carboxy-2naphthyl)aminobenzo(h)quin olin--ol-X-sulfonic acid.

3. The process as del-ined in claim l, wherein the color former is9-octadccylsulfonylaminobenzo(h)quinolin-6- ol-X-sulfonic acid.

4. The process as dened in claim l, wherein the color former is9,2-[7-(loctadecyl-5"-sulfo-2"benzimida zoyl) phenylcarb amyl lnaphthylaminobenzo (h quinolin-6- ol-X-sulfonic acid.

5. The process as defined in claim l, wherein the color former is9-E2-(4',6-dimethylamino1,3,5-triazinylamino l benzo (h)quinolin--ol-X-sulfonic acid.

6. A photographic silver-halide emulsion containing as a color former acompound of the following formula:

in which Y is selected from the class consisting of OH, NH2, and NHSOzR,R being selected from the class consisting of aliphatic and aromaticradicals, and Z is a member selected from the class consisting ofhydrogen, hydroxyl, an amino and an acylamino group Y being located onlyin one of the positions designated as 5- and 6- and Z being located onlyin one of the positions designated as 8-, 9- and l0-.

7. A photographic silver-halide emulsion containing as the color former9-(7carboxy2naphthyl)aminobenzo- (h) quinolin--ol-X-sulfonic acid.

8. A photographic silver-halide emulsion containing as the color former9-octadecylsulfonylaminobenzo(h)quinolin--ol-X-sulfonic acid.

9. A photographic silver-halide emulsion containing as the color former9,2[7-(1-octadecyl-5"sulfo-Z"- benzimidazoyl phenylcarbamyl]naphthylaminobcnzo (h) quinolin-6-Ol-X-sulfonic acid.

l0. A photographic silver-halide emulsion containing as the color former9-[2-(4,6dimethylaminol,3,5-tria- Zinylamino) l benzo (h)quinolin--ol-X-sulfonic acid.

1l. A photographic developer containing as a reducing agent a4,6-diamino metanilic acid, and as the color former a compound of thefollowing formula:

in which Y is selected from the class consisting of OH, NH2, and NHSOzR,R being selected from the class consisting of aliphatic and aromaticradicals, and Z is a member selected from the class consisting ofhydrogen, hydroxyl, an amino and an acylamino group Y being located onlyin one of the positions designated as 5- and 6- and Z being located onlyin one of the positions designated as 8, 9- and i0-, said compound beingfree from groups rendering the compound non-diffusing in photographicemulsions.

l2. A photographic developer containing as a reducing agent a4,6-diamino metanilic acid, and as the color former 9(7-carboxy-2naphthyl)aminobenzo(h)quino lin--ol-X-sulfonic acid.

i3. The process as dened in claim l, wherein Y is OH and Z is an aminogroup.

i4. The process as dened in claim l, wherein Y is OH and Z is anacylamino group.

l5. The process as defined in claim 1, wherein Y is OH which is locatediu the -position, and Z is an amino group located in the 9-postion.

16. The process as defined in claim 1, wherein Y is OH located in the-position, and Z is an acylamino group located in the 9postion.

17. The process as dened in claim l, wherein the color former contains asulfonic acid group.

18. The composition as dened in claim 6, wherein Y is OH, and Z is anamino group.

19. The composition as dened in claim 6, wherein Y is OH, and Z is anacylamino group.

20. The composition as dened in claim 6, wherein Y is OH which islocated in the 6positon and Z is au amino group located in the9-position.

21. The composition as defined in claim 6, wherein Y 18 is OH located inthe -position, and Z is group located in the 9postion.

22. The composition as defined in claim 11, wherein Y is OH, and Z is anamino group.

23. The composition as defined in claim 11, wherein Y is OH, and Z is anacylamino group.

24. The composition as defined in claim ll, wherein Y is OH located inthe 6-position and Z is an amino group located in the 9postion.

25. The composition as dened in clairnll, wherein Y is OH located in the6-position and Z is an acylamno group located in the 9postion.

an acylamino References Cited in the file of this patent UNITED STATESPATENTS 2,525,502 Tulagin et al Oct. 10, 1950

6. A PHOTOGRAPHIC SILVER-HALIDE EMULSION CONTAINING AS A COOLER FORMER ACOMPOUND OF THE FOLLOWING FORMULA: